SCIENCE & TECHNOLOGY

PRAVEEN THALLAPALLY/PNNL
NEW SORBENTS FOR
shown great potential
in recent years for
numerous adsorption

GREENER COOLING applications, such

as gas storage and
separation. Now, re-
searchers are studying
ACS MEETING NEWS: Custom porous materials
them for water-based
give eco-friendly adsorption chillers a boost adsorption cool-
MITCH JACOBY, C&EN CHICAGO ing. Theyre making
customized MOFs
designed to maximize
THE POSTDOC STANDING in the back of are available commercially but are used water-uptake capacity
the hot, crowded room fanned herself re- on a relatively small scale. They tend to be and cycling perfor-
peatedly. So did the national lab researcher very large and heavy and rely on common mance and testing
sitting in the front row, and the well- sorbents such as silica gel and zeolites, them in industrial
known academic sitting next to him. Ap- which exhibit mediocre water-uptake settings for long-term
parently the air-conditioning wasnt reach- properties. Implementing these devices stability.
ing the tiny meeting room at the far end of on a much larger scale calls for far superior MOFs are porous
a hard-to-find corridor in San Franciscos sorbents, such as metal-organic framework crystalline materials composed of metal
Moscone Center during last months (MOF) compounds. These materials have ions or metal clusters bridged by organic
American Chemical Society meeting. linking groups. They have generated
Had the system been working properly, intense scientific interest over the past
as it was in the rest of the giant convention SUPER SPONGE Custom-made Zr-based dozen years because of their outstanding
center, the room would have been cooled MOFs with carboxyl linker groups, such adsorption properties and numerous po-
by a heat-transfer process driven by cycling as the one shown here, take up record tential applications.
a refrigerant between gas and liquid states. quantities of water even at very low But so far, that interest has not led to
humidity levels (colored spheres
This kind of air-conditioning sys- indicate lattice void spaces). commercial application
tem, in which a fluid, typically of these materials,
a halocarbon, transfers heat says B. Peter McGrail,
by repeatedly being con- an environmental en-
densed and evapo- gineering specialist
rated, is ubiquitous. at Pacific Northwest
Its found in resi- National Laboratory
dential, commer- (PNNL). He sug-
cial, and industrial gests that adsorption
settings and used cooling is one of the
on land and sea and most likely near-term
in the air. commercial applications of
But it isnt the only MOFs.
game in town. Some
scientists, including some IN CONTRAST to con-
of the ones gathered in ventional condensation-
that stuffy room, are evaporation cooling sys-
investigating new ma- tems, adsorption chillers
terials for an alternative transfer heat through
heat-pump or air-cooling adsorption-desorption
system known as an ad- cycles. Both systems
sorption chiller. These sys- capitalize on the heat-
tems offer substantial energy transferringor
and environmental advan- coolingeffect
tages compared with brought about by
conventional cooling coupling an endo-
systems because thermic process
they require much with an exothermic
J. AM. C HEM. SOC.

less energy and, de- one. One step is

pending on applica- carried out inside
tion, can use water as the building or other in-
the refrigerant. sulated area to be cooled; the
Adsorption chillers other is done outside.

CEN.ACS.ORG 26 SEPTEMBER 8, 2014

 with roughly 1.4 g of water per gram of sor- in a brief review by Janiak and coworkers
bent (140% water by weight). That value is (Eur. J. Inorg. Chem. 2012, DOI: 10.1002/
more than four times as high as the loading ejic.201101056). Despite the degradation,
of conventional zeolites and silica gels. the team stresses that the ability to tune
The team finds, however, that upon MOF hydrophilicity by customizing the
repeated cycling, the water-uptake organic linkers and metal clusters gives
capacity of that material and all com- MOFs a clear advantage over conven-
mercially available MOFs decreases. tional zeolite-type sorbents, which are
Results of these studies are summarized less amenable to customization.

no smear, no smudge
No question.
CHILLAX In the case of adsorp-
Your lab revolves around ensuring accurate data and
PNNLs Feng tion systems, sending reliable results. Current methods for vial sample labeling
Zheng prepares
a MOF-filled
the refrigerant gas from
the house to a sorbent can be illegible or time consuming. No accurate and
adsorption heat
pump/chiller positioned outside, and efcient system for vial sample identication existed
for testing. adsorbing (trapping)
the gas there, releases until now. The Thermo Scientifc Virtuoso Vial
unwanted heat to the Identifcation System provides a fast, accurate,
atmosphere, thereby cooling the house.
Desorbing the refrigerant from the trap detailed and reproducible system for imaging
regenerates the sorbent and liberates the information directly onto a vial. Discover how much
gas so it can be sent back into the house for
the next cycle. more information, and condence, you can have
The desorption step requires heat input, in your sample ID.
but not much. The upshot is that adsorp-
tion chillers can run on very little energy.
These units can tap freely available solar
Expect more condence.
heat or low-temperature waste heat, con- See more at thermoscientic.com/virtuoso
tained, for example, in industrial plant
exhaust gases that are normally vented to
the atmosphere.
So how suitable are MOFs to this task? Permanent, solvent-
resistant identication
To date, only a handful of MOFs have been Text, graphics, barcodes
tested for water uptake and release. As and logos can all be
produced directly on the vial
expected, researchers have begun with
2014 Thermo Fisher Scientic Inc. All rights reserved. All trademarks

the ones available for purchase. At the

University of Birmingham, in England, for
are the property of Thermo Fisher Scientic and its subsidiaries.

example, mechanical engineer Raya Al-

Dadah and coworkers evaluated a copper
benzene tricarboxylate-based MOF known
as HKUST-1 and its iron analog. In terms
of water uptake, they found that the iron
compound isnt much better than silica gel, Choice of data input
but HKUST-1 showed an enhancement of Input data via touchscreen
or network, using standard
93% (Int. J. Heat Mass Transfer 2012, DOI: or custom templates
10.1016/j.ijheatmasstransfer.2012.07.068).
A similar study by Heinrich Heine
University Dsseldorf chemist Christoph
Janiak and coworkers found that a MOF
made from chromium and benzene dicar-
boxylate linkers (MIL-101) can be loaded

CEN.ACS.ORG 27 SEPTEMBER 8, 2014

 Thats the approach taken by Mircea
Dinc, a chemistry professor at Massachu-
setts Institute of Technology. His group
reasoned that increasing the hydrophilicity
of the interiors of MOF pores would broad-
en the range of atmospheric conditions,
such as relative humidity and temperature,
over which an adsorbent would function
well in a cooling application.
A RECENT STUDY suggests theyre on
the right track. The team made a series
of MOFs featuring pyrazolate-bridged
Zn2+ ions and a network of channels lined
with functionalized naphthalenediimide
groups. Those materials adsorbed water
efficiently when the relative humidity
was near 50%. But when the MOFs were
subsequently oxidized with dimethyldioxi-
fornia, Berkeley, stand out in this regard.
In that study, Hiroyasu Furukawa,
Omar M. Yaghi, and coworkers prepared
several MOFs featuring Zr6O4(OH)4 units
and variously shaped organic linkers. At
just 10% relative humidity, one of the
compounds, which contains fumaric acid
linkers (MOF-801), can take up 20 wt %
water. That value is three times as high as
a commercial zeolite used in adsorption
chillers. And a related compound with
multiringed linker groups (MOF-841)
soaks up a record-setting 40 wt % water at
roughly 30% humidity. The group reports
that both compounds can be regenerated
at room temperature and retain their
adsorption values for at least five cycles
(J. Am. Chem. Soc. 2014, DOI: 10.1021/
ja500330a).
three months and involved many tens of
thousands of cycles, Thallapally says. The
kilogram quantity of MOF loaded into the
industrial-sized unit maintained its water-
uptake and cooling capacities throughout
the trial run, demonstrating its durability.
The PNNL team is not yet sharing many
details of the MOF used in that test. The
group is awaiting patent approval. But
McGrail offers that the proprietary mate-
rial was designed with superhydrophilic
channels to provide high water capacity
and rapid adsorption-desorption kinetics.
He adds that using that MOF in a newly re-
designed chiller led to the most efficient,
compact, and lightweight chiller demon-
strated so far.
Now the PNNL team is working on a
prototype unit for the Navy. Specifically,
the researchers are working to design an

PRAVEEN THALLAPALLY/PN NL
adsorption chiller for refrigeration and
freezer applications to be used aboard sup-
ply vessels that deliver goods to the fleet.
Currently, ships burn diesel to power an
electric generator, to run a compressor, to
cool the cabin, and to operate refrigerators
and freezers for perishable cargo. With
an adsorption chiller, we can short-circuit
that process and save a lot of fuel, McGrail
says.
The idea is to tap the ships propulsion
system for waste heat thats normally
vented through the exhaust stack and use
it to drive a fluorocarbon-charged chiller
system. Fluorocarbons are far better suited
than water to reaching refrigeration tem-
peratures, so the team is evaluating these
kinds of refrigerants.
To help establish guidelines for making
high-performance sorbents for this unex-
plored application, the group just conduct-
ed a systematic study of the interactions
of a series of fluorocarbon refrigerants
with common MOFs. They examined the
influence of fluorine-metal interactions on
rane to coat the channels ORIENTATION Modeling Five adsorption-desorp- orienting the molecules in the MOF pores,
with sulfoxide and sulfone studies reveal the tion cycles in lab-sized test the effects of pore size and morphology,
groups, and thereby increase influence of fluorine-
metal interactions on the
equipment is a good start. and other factors regulating fluorocarbon
the channel hydrophilicity, preferred orientation of But far longer tests in an uptake in MOFs (Nat. Commun. 2014, DOI:
they soaked up water even a fluorinated refrigerant industrial rig are needed to 10.1038/ncomms5368).
when the humidity was as (gray, green, white) in a Cr- learn about the long-term Perhaps it was the novelty of the MOFs
low as 30% (Energy Envi- containing MOF (purple). stability of MOFs. That need for green air-conditioning idea that soon
ron. Sci. 2013, DOI: 10.1039/ prompted McGrail, Praveen caused the scientists in the stuffy San
c3ee40876k). K. Thallapally, and other Francisco meeting room to stop fanning
MOFs not only need to trap water ef- PNNL scientists to team up with Power themselves. More likely, it was the con-
ficiently to be useful in adsorption chillers, Partners Inc., an Athens, Ga.-based manu- ventional air-conditioning finally kicking
they must also retain their uptake capacity facturer of adsorption chillers for hospitals in and doing its job. Either way, fast-paced
and release the water with little energy in- and other institution-sized buildings. progress in customizing MOFs for refriger-
put. Two new MOFs reported recently in a In the summer of 2013, the team con- ant uptake is sure to help conference-goers
study conducted at the University of Cali- ducted a test that ran continuously for chill out sometime soon.

CEN.ACS.ORG 28 SEPTEMBER 8, 2014